CN103107366B - A kind of electrolyte thereof and power lithium-ion battery - Google Patents
A kind of electrolyte thereof and power lithium-ion battery Download PDFInfo
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- CN103107366B CN103107366B CN201210029083.8A CN201210029083A CN103107366B CN 103107366 B CN103107366 B CN 103107366B CN 201210029083 A CN201210029083 A CN 201210029083A CN 103107366 B CN103107366 B CN 103107366B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of electrolyte thereof, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 0.9 ~ 1.2mol/L, mixed solvent is by methyl ethyl carbonate EMC, propene carbonate PC, dimethyl carbonate DMC, ethylene carbonate EC, 1,3-propane sultone 1,3-PS and vinylene carbonate VC form, and EMC content is 40 ~ 60wt%, PC content is 5 ~ 15wt%, DMC content is 10 ~ 20wt%, EC content is 20 ~ 25wt%, 1,3-PS content is 0.5 ~ 2wt%, VC content is 0.5 ~ 2wt%.Electrolyte thereof provided by the invention is particularly useful for lithium manganate battery, adopts the lithium ion battery high and low temperature function admirable that electrolyte thereof provided by the invention is obtained, significantly can improve the cycle performance of lithium manganate battery.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of electrolyte thereof and adopt the power lithium-ion battery of this electrolyte.
Background technology
In recent years, along with the develop rapidly of lithium electrical travelling industry, lithium ion battery starts to enter electric motor car and Large-scale Mobile application of power field successively, but current lead-acid battery still dominate.Anode material for lithium-ion batteries is generally the transition metal oxide of cobalt acid lithium, LiMn2O4, lithium nickelate and all kinds of other element of doping.As electrokinetic cell, LiMn2O4 has given play to its advantage gradually, one of positive electrode becoming main flow.Lithium-ion battery electrolytes occupies an important position in lithium ion battery, and it directly affects the electrical property of lithium ion battery.The bath composition main electrolyte salt of current lithium ion battery and solvent composition, wherein solvent generally adopts carbonates mixed solvent as ethylene carbonate EC, propylene carbonate ester PC, methyl ethyl carbonate EMC, dimethyl carbonate DMC, diethyl carbonate DEC etc., and conventional electrolytic salt is lithium hexafluoro phosphate LiPF
6.
Lithium ion battery has the advantages such as voltage platform is high, memoryless performance, is widely applied.But simultaneously the range of application of lithium ion battery also receives the restriction of some conditions, namely the ambient temperature as application is one of key factor wherein.And the cycle performance of lithium manganate battery is also poor at present, remains to be further improved.
The lithium ion battery more employing LiPF of current battery manufacturers produce
6the electrolyte of/EC+DMC+EMC composition, wherein the volume ratio of EC, DMC and EMC is EC: DMC: EMC=1: 1: 1, though this electrolyte system has good security performance and active material capacity plays, but low and high temperature cycle performance is not ideal enough, time in the lithium ion battery of LiMn2O4 system, high temp effect performance is poor, can not meet the needs of power lithium-ion battery, be further improved.
Summary of the invention
The object of the present invention is to provide a kind of electrolyte thereof.
The present invention also aims to provide a kind of power lithium-ion battery.
In order to realize above object, the technical solution adopted in the present invention is: a kind of electrolyte thereof, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 0.9 ~ 1.2mol/L, described mixed solvent is by methyl ethyl carbonate EMC, propene carbonate PC, dimethyl carbonate DMC, ethylene carbonate EC, 1, 3-propane sultone 1, 3-PS and vinylene carbonate VC forms, wherein the mass percentage of methyl ethyl carbonate EMC is 40 ~ 60%, the mass percentage of propene carbonate PC is 5 ~ 15%, the mass percentage of dimethyl carbonate DMC is 10 ~ 20%, the mass percentage of ethylene carbonate EC is 20 ~ 25%, 1, 3-propane sultone 1, the mass percentage of 3-PS is 0.5 ~ 2%, the mass percentage of vinylene carbonate VC is 0.5 ~ 2%.
Preferably, lithium hexafluoro phosphate LiPF
6concentration be 1.0mol/L.
A kind of power lithium-ion battery, comprise electrode group and electrolyte thereof, described electrode group and electrolyte thereof are sealed in battery container, and described electrode group comprises positive pole, negative pole and barrier film, and described electrolyte thereof is by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 0.9 ~ 1.2mol/L, described mixed solvent is by methyl ethyl carbonate EMC, propene carbonate PC, dimethyl carbonate DMC, ethylene carbonate EC, 1, 3-propane sultone 1, 3-PS and vinylene carbonate VC forms, wherein the mass percentage of methyl ethyl carbonate EMC is 40 ~ 60%, the mass percentage of propene carbonate PC is 5 ~ 15%, the mass percentage of dimethyl carbonate DMC is 10 ~ 20%, the mass percentage of ethylene carbonate EC is 20 ~ 25%, 1, 3-propane sultone 1, the mass percentage of 3-PS is 0.5 ~ 2%, the mass percentage of vinylene carbonate VC is 0.5 ~ 2%.
Preferably, lithium hexafluoro phosphate LiPF
6concentration be 1.0mol/L.
Electrolyte thereof provided by the invention is by selecting the organic solvent of particular types, wherein ring-type EC has higher dielectric constant and viscosity, after adding low viscous chain DMC, the ionic conductivity of mixed solvent can be improved, improve the charge-discharge performance of lithium ion battery; PC (fusing point-49.2 DEG C, boiling point 241.7 DEG C, flash-point 132 DEG C), EMC (fusing point-55 DEG C) have lower fusing point, can widen the serviceability temperature scope of mixed solvent, increase the fail safe of battery; Because a large amount of PC easily forms the destruction that solvation lithium ion causes graphite cathode layer structure, not easily form effective solid electrolyte interface (SEI) film at graphite-like electrode surface, when PC content is more than 50%, graphite cathode, by ineffective, therefore will limit it and add content; In addition, vinylene carbonate (VC) is a kind of ring-type organic solvent containing unsaturated double-bond, can the stable SEI film-alkoxyl carbonic ester lithium of forming property in lithium ion battery first charge-discharge, coordinate 1,3-PS can be formed effectively again, fine and close, the stable and good SEI film of elasticity; Simultaneously VC, 1,3-PS one-tenth film potential all lower than the one-tenth film potential of above several solvent, thus reduce the loss of lithium ion, increase battery capacity, be conducive to the cycle life improving lithium ion battery.Reasonable mixture ratio between each organic solvent above, by the excellent film for additive that adds and high and low temperature performance additive, the advantage of each organic solvent can be given full play to and can mutually suppress respective shortcoming, electrolyte is made to play optimum chemical property, especially high and low temperature performance and cycle performance.After testing, with the high temperature 55 DEG C of power lithium-ion battery, 98% of 1C electric discharge releasing rated capacity prepared by electrolyte thereof of the present invention; Low temperature-20 DEG C, 1C electric discharge release rated capacity 77% ,-35 DEG C, 0.2C electric discharge release rated capacity 52%; After normal temperature 1C/1C circulates 300 weeks, capability retention is greater than 90%; After high temperature 55 DEG C, 1C/1C circulate 100 weeks, capability retention is greater than 85%.Above data illustrate, adopt the power lithium-ion battery high and low temperature function admirable that electrolyte thereof provided by the invention is obtained, the cycle performance of power lithium-ion battery significantly improves.
Electrolyte thereof provided by the invention is particularly useful for lithium manganate battery, adopt the power lithium-ion battery high and low temperature function admirable that electrolyte thereof provided by the invention is obtained, and significantly can improve the cycle performance of lithium manganate battery.
Embodiment
Below by way of specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
The electrolyte thereof that the present embodiment provides, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 0.9mol/L, mixed solvent is by methyl ethyl carbonate EMC, propene carbonate PC, dimethyl carbonate DMC, ethylene carbonate EC, 1, 3-propane sultone 1, 3-PS and vinylene carbonate VC forms, the mass percentage of methyl ethyl carbonate EMC is 40%, the mass percentage of propene carbonate PC is 15%, the mass percentage of dimethyl carbonate DMC is 20%, the mass percentage of ethylene carbonate EC is 24%, 1, 3-propane sultone 1, the mass percentage of 3-PS is 0.5%, the mass percentage of vinylene carbonate VC is 0.5%.
The preparation of the electrolyte thereof that the present embodiment provides: by methyl ethyl carbonate EMC, propene carbonate PC, dimethyl carbonate DMC, ethylene carbonate EC Homogeneous phase mixing in closed environment, then add lithium hexafluoro phosphate LiPF
6abundant mixing, finally adds 1,3-propane sultone 1,3-PS and vinylene carbonate VC mixes.
Randomly draw 1665132 batteries of 20 non-fluid injections, these 20 pieces of batteries are injected respectively the electrolyte thereof that the present embodiment provides in constant temperature and humidity room, according to a conventional method the battery of fluid injection is carried out aging, change into, degasification, sealing, partial volume, obtained power lithium-ion battery.
Embodiment 2
The electrolyte thereof that the present embodiment provides, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 1.0mol/L, mixed solvent is by methyl ethyl carbonate EMC, propene carbonate PC, dimethyl carbonate DMC, ethylene carbonate EC, 1,3-propane sultone 1,3-PS and vinylene carbonate VC forms, the mass percentage of methyl ethyl carbonate EMC is 60%, the mass percentage of propene carbonate PC is 5%, the mass percentage of dimethyl carbonate DMC is 11%, the mass percentage of ethylene carbonate EC is 20%, 1, the mass percentage of 3-propane sultone 1,3-PS is 2%, and the mass percentage of vinylene carbonate VC is 2%.
The preparation of the electrolyte thereof that the present embodiment provides is with embodiment 1.
Randomly draw 1665132 batteries of 20 non-fluid injections, these 20 pieces of batteries are injected respectively the electrolyte thereof that the present embodiment provides in constant temperature and humidity room, according to a conventional method the battery of fluid injection is carried out aging, change into, degasification, sealing, partial volume, obtained power lithium-ion battery.
Embodiment 3
The electrolyte thereof that the present embodiment provides, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 1.0mol/L, mixed solvent is by methyl ethyl carbonate EMC, propene carbonate PC, dimethyl carbonate DMC, ethylene carbonate EC, 1, 3-propane sultone 1, 3-PS and vinylene carbonate VC forms, the mass percentage of methyl ethyl carbonate EMC is 52%, the mass percentage of propene carbonate PC is 10%, the mass percentage of dimethyl carbonate DMC is 10%, the mass percentage of ethylene carbonate EC is 25%, 1, 3-propane sultone 1, the mass percentage of 3-PS is 1%, the mass percentage of vinylene carbonate VC is 2%.
The preparation of the electrolyte thereof that the present embodiment provides is with embodiment 1.
Randomly draw 1665132 batteries of 20 non-fluid injections, these 20 pieces of batteries are injected respectively the electrolyte thereof that the present embodiment provides in constant temperature and humidity room, according to a conventional method the battery of fluid injection is carried out aging, change into, degasification, sealing, partial volume, obtained power lithium-ion battery.
Embodiment 4
The electrolyte thereof that the present embodiment provides, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 1.2mol/L, mixed solvent is by methyl ethyl carbonate EMC, propene carbonate PC, dimethyl carbonate DMC, ethylene carbonate EC, 1, 3-propane sultone 1, 3-PS and vinylene carbonate VC forms, the mass percentage of methyl ethyl carbonate EMC is 47%, the mass percentage of propene carbonate PC is 10%, the mass percentage of dimethyl carbonate DMC is 20%, the mass percentage of ethylene carbonate EC is 20%, 1, 3-propane sultone 1, the mass percentage of 3-PS is 2%, the mass percentage of vinylene carbonate VC is 1%.
The preparation of the electrolyte thereof that the present embodiment provides is with embodiment 1.
Randomly draw 1665132 batteries of 20 non-fluid injections, these 20 pieces of batteries are injected respectively the electrolyte thereof that the present embodiment provides in constant temperature and humidity room, according to a conventional method the battery of fluid injection is carried out aging, change into, degasification, sealing, partial volume, obtained power lithium-ion battery.
For ease of comparing, the intercell adopted in above-described embodiment 1-4 all refers to the battery with a collection of same model (1665132S), said with a collection of preorder production technology referring to this batch of battery all, and uniquely different unlike the electrolyte injected in fluid injection operation.In the battery of this model, negative pole is composite graphite, just very LiMn2O4.
Power lithium-ion battery embodiment 1-embodiment 4 made carries out high temperature 55 DEG C, 1C electric discharge respectively,-20 DEG C, 1C electric discharge,-35 DEG C, 0.2C electric discharge, normal temperature (25 DEG C) 1C loop test, high temperature 55 DEG C, 1C loop test, test result is shown in Table 1.
The performance test results of the power lithium-ion battery that table 1 embodiment 1-4 obtains
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| 55 DEG C, 1C discharge capacitance | 97.6％ | 98.3％ | 97.8％ | 98.1％ |
| -20 DEG C, 1C discharge capacitance | 72.3％ | 77.1％ | 77.4％ | 73.6％ |
| -20 DEG C, 0.2C discharge capacitance | 89％ | 83％ | 89％ | 83％ |
| -35 DEG C, 0.2C discharge capacitance | 52％ | 44％ | 50％ | 42％ |
| 25 DEG C, efficiency after 1C 300 weeks circulation | 88.7％ | 89.5％ | 90.1％ | 89.2％ |
| 55 DEG C, efficiency after 1C 100 weeks circulation | 60％ | 85％ | 64.5％ | 81.5％ |
Can be found out by the test result of table 1, high and low temperature performance and the cycle performance of the power lithium-ion battery adopting electrolyte thereof provided by the invention to obtain are excellent.Electrolyte thereof provided by the invention is worthy of popularization.
Claims (2)
1. an electrolyte thereof, is characterized in that, by lithium hexafluoro phosphate LiPF
6form with mixed solvent, described mixed solvent is by methyl ethyl carbonate EMC, propene carbonate PC, dimethyl carbonate DMC, ethylene carbonate EC, 1, 3-propane sultone 1, 3-PS and vinylene carbonate VC forms, wherein the mass percentage of methyl ethyl carbonate EMC is 40 ~ 52%, the mass percentage of propene carbonate PC is 10 ~ 15%, the mass percentage of dimethyl carbonate DMC is 10 ~ 20%, the mass percentage of ethylene carbonate EC is 20 ~ 25%, 1, 3-propane sultone 1, the mass percentage of 3-PS is 0.5 ~ 2%, the mass percentage of vinylene carbonate VC is 0.5 ~ 2%,
Lithium hexafluoro phosphate LiPF
6concentration be 1.0mol/L.
2. a power lithium-ion battery, comprise electrode group and electrolyte thereof, described electrode group and electrolyte thereof are sealed in battery container, described electrode group comprises positive pole, negative pole and barrier film, it is characterized in that, described electrolyte thereof is electrolyte according to claim 1.
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| CN201210029083.8A CN103107366B (en) | 2012-02-09 | 2012-02-09 | A kind of electrolyte thereof and power lithium-ion battery |
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| CN103107366B true CN103107366B (en) | 2015-12-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111342132A (en) * | 2020-03-04 | 2020-06-26 | 河南省法恩莱特新能源科技有限公司 | Lithium manganate multiplying power lithium ion battery electrolyte and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413970B (en) * | 2013-08-06 | 2016-06-22 | 朝阳光达化工有限公司 | Low-temperature type carbonic ester lithium battery electrolyte |
| CN103700884A (en) * | 2013-08-14 | 2014-04-02 | 江西世纪长河新电源有限公司 | Electrolyte of power lithium ion secondary battery |
| US20210111432A1 (en) * | 2018-03-23 | 2021-04-15 | Maxwell Technologies, Inc. | Electrolyte additives and formulations for energy storage devices |
| CN112382791A (en) * | 2020-11-24 | 2021-02-19 | 河南省法恩莱特新能源科技有限公司 | Electrolyte for TWS Bluetooth headset lithium ion battery, preparation method of electrolyte and lithium ion battery |
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| CN1925207A (en) * | 2006-09-20 | 2007-03-07 | 广州市天赐高新材料科技有限公司 | High rate electrolyte for lithium ion battery |
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| CN1787273A (en) * | 2004-12-08 | 2006-06-14 | 天津力神电池股份有限公司 | Low temp. electric liquid for battery |
| CN1925207A (en) * | 2006-09-20 | 2007-03-07 | 广州市天赐高新材料科技有限公司 | High rate electrolyte for lithium ion battery |
| CN101013763A (en) * | 2007-02-16 | 2007-08-08 | 天津力神电池股份有限公司 | Non-aqueous electrolyte and secondary cell of non-aqueous electrolyte |
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Address after: 454191 Henan Province, Jiaozuo City Station area coke Rd Patentee after: Duofudo New Material Co.,Ltd. Address before: 454191, Feng County, Henan Province, Jiaozuo Feng Feng Chemical Industry Zone Patentee before: DO-FLUORIDE CHEMICALS Co.,Ltd. |